CN108946808A - A kind of full-inorganic caesium-bismuth/antimony halide perovskite is nanocrystalline and preparation method thereof - Google Patents
A kind of full-inorganic caesium-bismuth/antimony halide perovskite is nanocrystalline and preparation method thereof Download PDFInfo
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- CN108946808A CN108946808A CN201810659534.3A CN201810659534A CN108946808A CN 108946808 A CN108946808 A CN 108946808A CN 201810659534 A CN201810659534 A CN 201810659534A CN 108946808 A CN108946808 A CN 108946808A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 11
- -1 antimony halide Chemical class 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 50
- 239000013081 microcrystal Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000003205 fragrance Chemical class 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000002604 ultrasonography Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229940071870 hydroiodic acid Drugs 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
- C01G29/006—Compounds containing, besides bismuth, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/002—Compounds containing, besides antimony, two or more other elements, with the exception of oxygen or hydrogen
- C01G30/003—Compounds containing, besides antimony, two or more other elements, with the exception of oxygen or hydrogen containing halogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides that a kind of full-inorganic caesium-bismuth/antimony halide perovskite is nanocrystalline and preparation method thereof, which first uses wet process or solid-phase synthesis that Cs is prepared3M2X9Micro crystal material, then by Cs3M2X9Micro crystal material carries out ultrasonic removing, obtains Cs after last centrifugal purification3M2X9It is nanocrystalline.By the optimization to material component and preparation process, nanocrystalline size can be adjustable within the scope of 2-100nm.This method is easy to operate quickly, favorable reproducibility.The Cs prepared using this method3M2X9Nanocrystalline narrow size distribution, stability are high, can be used for making photoelectric device, are applied to the fields such as solar cell, photodetector, photocatalysis and photoelectrocatalysis.
Description
Technical field
The invention belongs to novel inorganic field of nano material preparation, and in particular to a kind of full-inorganic Cs3M2X9Perovskite nanometer
Crystalline substance and preparation method thereof.
Background technique
Based on APbX3(A:Cs, CH3NH3(MA)；X:Cl, Br, I) lead-based perovskite it is nanocrystalline have it is biggish absorb cut
The advantages that face, high fluorescence quantum efficiency and tunable luminous within the scope of entire ultraviolet/visible light, in recent years by
Very extensive concern.However, this perovskite is nanocrystalline containing toxic element lead, this perovskite nanometer is significantly limited
Brilliant development, in addition to this, the nanocrystalline stability of this perovskite is also relatively poor.Therefore, synthesis is less toxic, high stability
Nanocrystalline become of perovskite works as previous big research hotspot.Bismuth or antimony based perovskite body phase material have been reported in recent years, due to
They have toxicity more lower than lead-based perovskite and higher stability, therefore by certain attention.But it is directed to bismuth or antimony
The nanocrystalline research of based perovskite is then relatively fewer.The nanocrystalline method of this perovskite-like is synthesized at present is concentrated mainly on solvent resistant
Method, hot injection method, operation is relatively complicated, and reaction condition is more harsh, and reproducibility is relatively poor.
Summary of the invention
Based on this, the present invention provides a kind of full-inorganic caesium-bismuth/nanocrystalline preparation method of antimony halide perovskite, the party
Method is easy to operate quickly, favorable reproducibility.
Full-inorganic caesium-bismuth/nanocrystalline preparation method of antimony halide perovskite of the present invention the following steps are included:
S1: preparation Cs3M2X9Micro crystal material
Cs is prepared using wet process or solid-phase synthesis3M2X9Micro crystal material.
S2: preparation Cs3M2X9It is nanocrystalline
By Cs3M2X9Micro crystal material is distributed in organic solvent, ultrasonic removing is then carried out, most afterwards through centrifugal purification upper
Cs is obtained in clear liquid3M2X9It is nanocrystalline.
Wherein, M is trivalent metal, one of X Cl, Br, I or a variety of mixing.
Compared with the existing technology, preparation method of the invention is by Cs3M2X9Micro crystal material carries out ultrasonic removing, can synthesize
Out narrow size distribution, defect concentration it is low, without the high Cs of toxicity Pb element, stability3M2X9Full-inorganic perovskite is nanocrystalline, and
It is easy to operate quick, favorable reproducibility.
Further, the M is one or both of Bi, Sb mixing.
Further, wet process described in step S1 is to aoxidize the halide metal salt containing M element, carbonate or metal
Object is dissolved separately in solvent with containing caesium raw material, obtains two kinds of precursor solutions；Both precursor solutions are quickly mixed, are stirred
It is largely precipitated after mixing, Cs will be obtained after precipitating drying3M2X9Micro crystal material.
Further, the solvent in the Moist chemical synthesis is ethyl alcohol, methanol, DMF, DMSO, acetonitrile, water, halogen acids equal solvent
One or more of mixing.
Further, solid-phase synthesis described in step S1 be will the halide metal salt containing M element and CsX normal-temperature solid-phase
Stirring is sintered to obtain Cs in 800 DEG C of following temperature3M2X9Micro crystal material.
Further, dispersing agent can be added in organic solvent described in step S2.
Further, the organic solvent is halogenated alkane, alkane, aromatic hydrocarbon, alcohols, lipid, aldehydes, one in organic acid
Kind or several mixing.Such organic solvent can disperse Cs well3M2X9Micro crystal material, while will not be with Cs3M2X9Crystallite material
Material reacts, changes its structure.
Further, the dispersing agent is the mixing of one or more of oleic acid, propionic acid equal solvent.It can be subtracted using dispersing agent
Few nanocrystalline reunion, improves dispersion performance.
The Cs being prepared according to the above method3M2X9It is nanocrystalline to can be used for making photoelectric device, be applied to solar cell,
The fields such as photodetector, photocatalysis and photoelectrocatalysis.
Detailed description of the invention
Fig. 1 is Cs3Bi2Cl9The XRD diagram of micro crystal material；
Fig. 2 is Cs3Bi2Cl9The SEM of micro crystal material schemes；
Fig. 3 is Cs3Bi2Cl9Nanocrystalline TEM figure；
Fig. 4 is Cs3Bi2Br9The XRD diagram of micro crystal material；
Fig. 5 is Cs3Bi2Br9The SEM of micro crystal material schemes；
Fig. 6 is Cs3Bi2Br9Nanocrystalline TEM figure；
Fig. 7 is Cs3Bi2I9The XRD diagram of micro crystal material；
Fig. 8 is Cs3Bi2I9The SEM of micro crystal material schemes；
Fig. 9 is Cs3Bi2I9Nanocrystalline TEM figure；
Figure 10 is Cs3Bi2I9Nanocrystalline XRD diagram；
Figure 11 is Cs3Sb2I9The XRD diagram of micro crystal material；
Figure 12 is Cs3Sb2I9The SEM of micro crystal material schemes；
Figure 13 is Cs3Sb2I9Nanocrystalline TEM figure.
Specific embodiment
The present invention prepares Cs using ultrasonic stripping means3M2X9It is nanocrystalline, can synthesize narrow size distribution, stability it is high,
The Cs of opto-electronic device can be used to make3M2X9Full-inorganic perovskite is nanocrystalline, easy to operate quick, favorable reproducibility.Below by way of
Specific embodiment simultaneously carrys out the technical solution that the present invention will be described in detail in conjunction with attached drawing.
Embodiment 1
S1-1: preparation Cs3Bi2Cl9Micro crystal material
By 3mmol CsCl, 2mmol BiCl3It is ground at normal temperature after mixing, obtains Cs3Bi2Cl9Micro crystal material.
S2-1: preparation Cs3Bi2Cl9It is nanocrystalline
Take 0.2g Cs3Bi2Cl9Micro crystal material is dispersed in 20mL chloroform, ultrasound 20 minutes (4 under 300W ultrasonic power
Second ultrasound is spaced for 4 seconds).Then at 500 rpm after low-speed centrifugal, lower end precipitating is discarded.Then by supernatant 3000rpm's
High speed centrifugation under revolving speed discards precipitating, Cs is obtained in supernatant3Bi2Cl9It is nanocrystalline.
Fig. 1 is please referred to, which is Cs3Bi2Cl9The XRD spectrum of micro crystal material, the Cs that the present invention prepares3Bi2Cl9's
Characteristic diffraction peak and ICSD#2067Cs3Bi2Cl9Card image perfection coincide, it was demonstrated that has obtained pure Cs3Bi2Cl9.Please join simultaneously
According to Fig. 2, which is Cs3Bi2Cl9The SEM of micro crystal material schemes.Fig. 2 shows, the Cs that the present invention prepares3Bi2Cl9Micro crystal material
Size is mainly distributed between 2-8 μm.
Referring to figure 3., which is Cs3Bi2Cl9Nanocrystalline TEM figure.Fig. 3 shows, what the present invention prepared
Cs3Bi2Cl9Nanocrystalline size is mainly distributed between 20-70nm.
Embodiment 2
S1-2: preparation Cs3Bi2Br9Micro crystal material
By 1.5mmol Cs2CO3, 2mmol BiBr3It is dissolved separately in 10mL hydrobromic acid, stirs 1 hour, make at 100 DEG C
It is sufficiently dissolved, and obtains two kinds of precursor solutions.It filters, obtains a large amount of after two kinds of precursor solutions are quickly mixed under room temperature
Precipitating, is dried to obtain Cs for precipitating in baking oven3Bi2Br9Micro crystal material.
S2-2: preparation Cs3Bi2Br9It is nanocrystalline
Take 0.2g Cs3Bi2Br9Micro crystal material is dispersed in 20mL chloroform, ultrasound 20 minutes (4 under 300W ultrasonic power
Second ultrasound is spaced for 4 seconds).Then at 500 rpm after low-speed centrifugal, lower end precipitating is discarded, Cs is obtained in supernatant3Bi2Br9
It is nanocrystalline.
Referring to figure 4., which is Cs3Bi2Br9The XRD spectrum of micro crystal material, the Cs that the present invention prepares3Bi2Br9's
Characteristic diffraction peak and ICSD#1142Cs3Bi2Br9Card image is coincide, it was demonstrated that has obtained pure Cs3Bi2Br9.Referring to figure
5, which is Cs3Bi2Br9The SEM of micro crystal material schemes.Fig. 5 shows, the Cs that the present invention prepares3Bi2Br9Micro crystal material size
It is mainly distributed between 2-7 μm.
Fig. 6 is please referred to, which is Cs3Bi2Br9Nanocrystalline TEM figure.Fig. 6 shows, what the present invention prepared
Cs3Bi2Br9Nanocrystalline size is mainly distributed between 2-5nm.
Embodiment 3
S1-3: preparation Cs3Bi2I9Micro crystal material
By 3mmol CsI, 2mmol BiI3It is dissolved separately in 10mL hydroiodic acid, is stirred 1 hour at 100 DEG C, fill it
Divide dissolution, obtains two kinds of precursor solutions.It filters after two kinds of precursor solutions are quickly mixed under room temperature, is largely sunk
It forms sediment, precipitating is dried to obtain Cs in baking oven3Bi2I9Micro crystal material.
S2-3: preparation Cs3Bi2I9It is nanocrystalline
Take 0.2g Cs3Bi2I9Micro crystal material is dispersed in 20mL chloroform, ultrasound (4 seconds 20 minutes under 300W ultrasonic power
Ultrasound is spaced for 4 seconds).Then bottom precipitation is discarded after low-speed centrifugal at 500 rpm, Cs is obtained in supernatant3Bi2I9Nanometer
It is brilliant.
Fig. 7 is please referred to, which is Cs3Bi2I9The XRD spectrum of micro crystal material, the Cs that the present invention prepares3Bi2I9Spy
Levy diffraction maximum and PDF#23-0847Cs3Bi2I9Card image is coincide, it was demonstrated that has obtained pure Cs3Bi2I9.Referring to Fig. 8,
The figure is Cs3Bi2I9The SEM of micro crystal material schemes.Fig. 8 shows, the Cs that the present invention prepares3Bi2I9Micro crystal material piece farmland is 2-5
μm, thickness is about 500nm.
Referring to Fig. 9 and Figure 10, the present invention has prepared the relatively pure Cs of structure3Bi2I9It is nanocrystalline, and its size
About 13nm.
Embodiment 4
S1-4: preparation Cs3Sb2I9Micro crystal material
By 3mmol CsI, 1mmol Sb2O3It is dissolved separately in 10mL hydroiodic acid, is stirred 1 hour at 100 DEG C, fill it
Divide dissolution, obtains two kinds of precursor solutions.It filters after two kinds of precursor solutions are quickly mixed under room temperature, is largely sunk
It forms sediment, precipitating is dried to obtain Cs in baking oven3Sb2I9Micro crystal material.
S2-4: preparation Cs3Sb2I9It is nanocrystalline
Take 0.2g Cs3Sb2I9Micro crystal material is dispersed in 20mL chloroform, ultrasound (4 seconds 20 minutes under 300W ultrasonic power
Ultrasound is spaced for 4 seconds).Then bottom precipitation is discarded after low-speed centrifugal at 500 rpm, Cs is obtained in supernatant3Sb2I9Nanometer
It is brilliant.
Figure 11 is please referred to, which is Cs3Sb2I9The XRD spectrum of micro crystal material, the Cs that the present invention prepares3Sb2I9Spy
Levy diffraction maximum and ICSD#300002Cs3Sb2I9Card image is coincide, it was demonstrated that has obtained pure Cs3Sb2I9.Referring to figure
12, which is Cs3Sb2I9The SEM of micro crystal material schemes.Figure 12 shows, the Cs that the present invention prepares3Sb2I9Micro crystal material piece farmland
It is 1-5 μm, thickness is about 500nm.Please refer to Figure 13, Cs prepared by the present invention3Sb2I9Nanocrystalline size is 12-30nm.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.
Claims (6)
1. a kind of full-inorganic caesium-bismuth/nanocrystalline preparation method of antimony halide perovskite, comprising the following steps:
S1: preparation Cs3M2X9Micro crystal material
Cs is prepared using wet process or solid-phase synthesis3M2X9Micro crystal material；
S2: preparation Cs3M2X9It is nanocrystalline
By Cs3M2X9Micro crystal material is distributed in organic solvent, ultrasonic removing is then carried out, most afterwards through centrifugal purification in supernatant
In obtain Cs3M2X9It is nanocrystalline；
Wherein, M is trivalent metal, one of X Cl, Br, I or a variety of mixing.
2. preparation method according to claim 1, it is characterised in that: the M is one or both of Bi, Sb mixing.
3. preparation method according to claim 1, it is characterised in that: wet process described in step S1 is, by the halogen containing M element
Compound metal salt, carbonate or metal oxide are dissolved separately in solvent with containing caesium raw material, obtain two kinds of precursor solutions；It will
Both precursor solutions are largely precipitated after being sufficiently mixed, and will obtain Cs after precipitating drying3M2X9Micro crystal material.
4. preparation method according to claim 1, it is characterised in that: solid-phase synthesis described in step S1 is will be containing M member
The halide metal salt and CsX normal-temperature solid-phase of element stir or are sintered to obtain Cs in 800 DEG C of following temperature3M2X9Micro crystal material.
5. preparation method according to claim 1, it is characterised in that: the organic solvent is halogenated alkane, alkane, fragrance
The mixing of one or more of hydrocarbon, alcohols, lipid, aldehydes, organic acid.
6. a kind of full-inorganic caesium-bismuth/antimony halide perovskite is nanocrystalline, it is characterised in that: made by any one of claim 1 to 5
Preparation Method is prepared.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482596A (en) * | 2019-07-23 | 2019-11-22 | 中国计量大学 | A kind of bismuth titanates nanometer piece preparation method of double lanthanide ion codopes |
| CN110937623A (en) * | 2019-12-03 | 2020-03-31 | 吉林大学 | Simple synthetic CsAgCl2Method for pure-phase inorganic non-lead perovskite |
| CN111790408A (en) * | 2020-07-20 | 2020-10-20 | 山东大学 | Bismuth/antimony-based perovskite, photocatalytic material, and preparation method and application thereof |
| CN112774719A (en) * | 2021-01-22 | 2021-05-11 | 暨南大学 | Novel limited-area inorganic perovskite Cs3Bi2Br9Photocatalytic film and preparation method and application thereof |
| CN112798545A (en) * | 2019-11-13 | 2021-05-14 | 中国科学院大连化学物理研究所 | Inorganic perovskite material with continuously adjustable absorption spectrum and preparation and application thereof |
| CN113134376A (en) * | 2021-04-19 | 2021-07-20 | 铜陵博雅渡业新材料科技有限公司 | Cs3Bi2Cl9(PQDs) supported nanosheet self-assembled bismuth oxycarbonate microsphere visible-light-driven photocatalyst and preparation method thereof |
| CN114437722A (en) * | 2022-01-27 | 2022-05-06 | 江西理工大学 | Rare earth-based perovskite CsTmCl3Microcrystalline material and preparation method and application thereof |
| CN114560500A (en) * | 2022-02-18 | 2022-05-31 | 河北工业大学 | Non-lead perovskite material and preparation method and application thereof |
| CN114590836A (en) * | 2022-03-08 | 2022-06-07 | 中国科学技术大学 | Lead-free halide perovskite nanocrystal, liquid-phase synthesis method thereof and application of perovskite nanocrystal in photoelectric detector |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482596A (en) * | 2019-07-23 | 2019-11-22 | 中国计量大学 | A kind of bismuth titanates nanometer piece preparation method of double lanthanide ion codopes |
| CN110482596B (en) * | 2019-07-23 | 2022-07-08 | 中国计量大学 | Preparation method of double lanthanide ion co-doped bismuth titanate nanosheet |
| CN112798545B (en) * | 2019-11-13 | 2022-03-29 | 中国科学院大连化学物理研究所 | Inorganic perovskite material with continuously adjustable absorption spectrum and preparation and application thereof |
| CN112798545A (en) * | 2019-11-13 | 2021-05-14 | 中国科学院大连化学物理研究所 | Inorganic perovskite material with continuously adjustable absorption spectrum and preparation and application thereof |
| CN110937623A (en) * | 2019-12-03 | 2020-03-31 | 吉林大学 | Simple synthetic CsAgCl2Method for pure-phase inorganic non-lead perovskite |
| CN111790408A (en) * | 2020-07-20 | 2020-10-20 | 山东大学 | Bismuth/antimony-based perovskite, photocatalytic material, and preparation method and application thereof |
| CN112774719A (en) * | 2021-01-22 | 2021-05-11 | 暨南大学 | Novel limited-area inorganic perovskite Cs3Bi2Br9Photocatalytic film and preparation method and application thereof |
| CN112774719B (en) * | 2021-01-22 | 2023-08-04 | 暨南大学 | Limited domain inorganic perovskite Cs 3 Bi 2 Br 9 Photocatalytic film and preparation method and application thereof |
| CN113134376A (en) * | 2021-04-19 | 2021-07-20 | 铜陵博雅渡业新材料科技有限公司 | Cs3Bi2Cl9(PQDs) supported nanosheet self-assembled bismuth oxycarbonate microsphere visible-light-driven photocatalyst and preparation method thereof |
| CN113134376B (en) * | 2021-04-19 | 2023-01-31 | 铜陵博雅渡业新材料科技有限公司 | Cs 3 Bi 2 Cl 9 (PQDs) supported nanosheet self-assembled bismuthyl carbonate microsphere visible-light-driven photocatalyst and preparation method thereof |
| CN114437722A (en) * | 2022-01-27 | 2022-05-06 | 江西理工大学 | Rare earth-based perovskite CsTmCl3Microcrystalline material and preparation method and application thereof |
| CN114437722B (en) * | 2022-01-27 | 2023-05-16 | 江西理工大学 | Rare earth based perovskite CsTmCl 3 Microcrystalline material and preparation method and application thereof |
| CN114560500A (en) * | 2022-02-18 | 2022-05-31 | 河北工业大学 | Non-lead perovskite material and preparation method and application thereof |
| CN114560500B (en) * | 2022-02-18 | 2024-04-09 | 河北工业大学 | Leadless perovskite material and preparation method and application thereof |
| CN114590836A (en) * | 2022-03-08 | 2022-06-07 | 中国科学技术大学 | Lead-free halide perovskite nanocrystal, liquid-phase synthesis method thereof and application of perovskite nanocrystal in photoelectric detector |
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